DK175476B1 - Photoactivator dye composition, method of preparation thereof and detergent composition containing the same - Google Patents

Description

DK 175476 B1

The present invention relates to a photoactivator dye composition which is particularly suitable for use in detergent compositions, a process for preparing this photoactivator composition and detergent compositions containing the same.

U.S. Patent No. 3,927,967 discloses the use of photoactivator dyes, such as phthalocyanine dyes, in detergents.

Various photoactivator dyes are capable of absorbing electromagnetic radiation in the visible-light region and emit the absorbed energy quantum in a form which provides bleaching effect on clothing.

It is believed that these energy quantities form singlet oxygen which is oxidatively active. Some photoactivators, such as zinc phthalocyanine I sulfonate (ZPS) and aluminum phthalocyanine sulfonate (APS), have been found in commercial use in granular detergent compositions.

However, when used in detergent compositions, phthalocyanine dyes exhibit certain disadvantages which have not been properly addressed so far. One such disadvantage is that the particles in which the dyes are incorporated do not dissolve sufficiently quickly upon contact with water to avoid dye staining. Such contact occurs with particular probability in hand washing situations, or when a dispenser is used which is placed in the drum of the washing machine together with the clothing; such a stain can even occur when the dye-containing detergent composition is supplied from a dispenser of a typical European washing machine.

It has been attempted to spray spray-dried detergent grains into a solution of the dye, but it has been found that the grains thus treated do not dissolve quickly enough to avoid dye-staining the clothing. The current development goes against higher density detergent grains, which grains are even less suitable as carriers for the dye.

In the best photoactivator dye addition pathway available today, 35 comprises spraying low-mass grains with a color-in-solution solution, which grains are subsequently dry blended with the basic granules of the composition. Although these low-mass-rich grains I dissolve faster than the basic grains, they do not dissolve quickly enough to prevent dye staining of clothing under different washing conditions. |

In the present invention, phthalocyanine dyes relate to I

For use in detergents, which dyes are peculiar to I

5 being encapsulated in an encapsulating material which is rapidly dissolved in I

In cold water. The encapsulating material is preferably not dissolved in an I

In nonionic surfactant. IN

In preferred phthalocyanine dyes, zinc phthalocyanine sulfonate is I

In 10 (ZPS) and aluminum phthalocyanine sulfonate (APS). IN

Preferred encapsulating materials include gelatin, especially I

In low bloom gelatines and mixtures I

of gelatin and sugar. IN

I 15

The present invention also relates to a process for the preparation

In the position of encapsulated photoactivator compositions, which I

In the method:

In the first, the photoactivator dye is dissolved in an aqueous medium, I

In the 2nd, the photoactivator dye solution is mixed in an aqueous I

In solution of the encapsulating material, I

3. That the resulting mixture is then converted into droplets with an I

In average size not exceeding 500 µm and I

In 4. that the moisture content of the particles is reduced to a value I

In between 2% and 12% by weight. IN

I 30

The invention further relates to granular detergent compositions which I

You contain the encapsulated phthalocyanine dyes. IN

In the Photoactivator dye composition of the invention, I comprises

In 35 microcapsules of a solid solution of a water-soluble photoactiv I

In liquid dye (solute) in an encapsulating material (solvent I)

Medium) which is rapidly soluble in cold water, which microcapsules

I by weight of the capsules comprises:

B) a) from 1% to 60% photoactivator dye, preferably from 1% to 40%, b) from 38% to 97% encapsulating material, and 5 c) from 2% to 12% water, preferably from 2% to 5%.

The term "microcapsule is" means capsules having an average particle size not exceeding 500 microns, and preferably having an average particle size of from 50 microns to 450 microns.

To assess the ability of a material to dissolve in cold water, the following experiments can be performed: A Sotax AT6 solution apparatus is used in which the stirring rate is adjusted to 150 rpm. min., using I bucket stirring rods. Pour 1000 ml buffer of pH 9.5 into each 1 polycarbonate beaker and keep the buffer at 20 ° C. 0.05 g of material is added to the buffer solution. Stirring at the indicated 20 conditions, sample volumes of 3 ml are taken from the solution at 15-second intervals for two minutes; the absorbance of each sample amount I is measured at 669 nm. According to this experiment, suitable materials have the following in solution profile: I 25> 80% dissolved after 30 seconds I> 95% dissolved after 60 seconds I 100% dissolved after 120 seconds In the encapsulating material of the photoactivator dye composition, I 30 is preferably not dissolved in nonionic surfactants.

In Modern detergent compositions, in fact, almost non-ionic surfactants typically contain from about 1% to about 12%. In most cases, this non-ionic surfactant is sprayed onto the base grain of the detergent composition. During storage, the non-ionic surfactant freely migrates through the mass of the detergent composition, especially if the non-ionic surfactant is liquid at the storage temperature.

I DK 175476 B1 B Because phthalocyanine dyes are highly soluble in non-ionic |

B surfactants, these dyes also migrate and become adsorbed

B right on the basic grains rather than on the low-mass grains. As in

As a result, the appearance of the detergent composition becomes rather I

B 5 unappealing. In addition, the solution of the dye becomes you

B associated with the dissolution of the base grains rather than with the very I

B faster dissolution of the low-mass grains. IN

B The insolubility of the encapsulating materials required herein is non-I

B 10 ionic surfactant can be evaluated by the following experiments:

B 0.05 g Encapsulating material is added to 50 ml of "Dobanol" 45 E ^ at 1

B 40 ° C ("Dobanol" 45 E 1 is an alkyl alcohol ethylene oxide condensate;

B predominantly linear primary Cj ^ / Cjg alcohol with an average of 7 I

B (ethylene oxide groups). IN

B The temperature is kept at 40 ° C for one hour. The extent of resolution is measured

B at the absorbance at 669 nm, and according to this measure there should be no I

B any sign of resolution after one hour. IN

I 20 I

B Examples of suitable water-soluble photoactivators include I

B easin, rose-Bengal, fluorescein, chlorophyll, metal-free porphyrin and I

B polyvalent metal ion complexes of sulfonated phthalocyanine, especially without I

B unsulfonated phthalocyanine. IN

I 25 I

B 24-3 + 1

Examples of suitable polyvalent metal ions include Zn, Al, I

B 2+ I

Mn, etc. Preferred photoactivator dyes are zinc phthalocyanine-I

B sulfonate (ZPS), aluminum phthalocyanine fulphonate (APS) and mixtures I

thereof. Oise dyes are commercially available as sodium salts. IN

I 30 I

In a preferred embodiment, the m croc capsules comprise from 5 l

In weight percent to 30 percent by weight photoactivator dye. IN

Examples of suitable encapsulating materials include gelatin, I

In 35 hydrolyzed gelatin and hind-forming carbohydrates. Preferred I

In encapsulating materials, hydrolyzed gelatin and hind-forming I

In carbohydrates, including dextrin and gum arabic. IN

In the photoactivator dye composition described above, you can

B1 is prepared by a process comprising: (1) dissolving the photoactivator dye in an aqueous medium, (2) mixing the photoactivator dye solution with an aqueous solution of the encapsulating material, (3) converting the thus obtained mixture into droplets with a average particle size not exceeding 500 µm and 10 (4) reducing the moisture content of the particles to a value of between 2% and 12% by weight to form a solid solution of the photoactivator dye in the encapsulating material.

15

Preferably, the encapsulating material should have a substantially higher molecular weight than the photoactivator dye. Thus, if the size of the photoactivator dye molecules is less than ca. 0.5 of that of the encapsulating material, a comprehensive interstitial solid solution is obtained, i. a solid solution in which the dissolved molecules occupy the interstitial space of the solvent lattice.

The formation of such an interstitial solid solution appears to contribute substantially to the rapid release of the photoactivator dye in a finely dispersed form when the capsules are contacted with water.

The conversion of the mixture into droplets and the reduction in the moisture content of the droplets is preferably carried out by a spray-drying method.

In a preferred embodiment of the process according to the invention, the mixture is spray dried at an elevated temperature of less than 100 ° C with the introduction of a fine powder into the spray drying zone as described in US Patent No. 2,756,177. The fine powder may be silicate or finely divided corn starch, preferably finely divided corn starch.

In another preferred embodiment, the mixture is spray dried at I DK 175476 B1

B a temperature above 100 ° C. IN

B In a preferred embodiment, sugar (sucrose) or I can

B glycose syrup is added to the mixture to be spray dried

B 5 reduction of the viscosity of the mixture, the weight ratio of I

B encapsulating material and sugar content is at least 35:65, preferably I

B 50:50.

B An oil, such as coconut oil, is preferably incorporated into the mixture, I

B 10 to be spray dried, in the form of an emulsion. The presence of

The oil facilitates the formation of droplets by spray drying the mixture

B gene and amounts of from 3% to 20% by weight can be used

B is preferably 5% to 10% by weight; the most preferred I

The amount of oil is 5% by weight.

I 15 B The solids content of the mixture to be spray dried may vary

B within wide limits, but the viscosity is preferably kept within I

B for the range from 0.07 Ns / m2 (70 cp) to 0.2 Ns / m2 (200 cp) at 1

At 60 ° C.

I 20 B Detergent compositions of the invention preferably contain in the aforementioned photoactivator dye composition in an amount of from 2 ppm to 1000 ppm pure photoactivator dye by weight of the detergent composition.

I 25

The detergent composition further contains typical detergent components, e.g. organic surfactants, detergent builders, in traditional detergent auxiliaries, etc. Organic surfactants can occur in the range of from 1% to 60% of the total composition.

I 30

Detergent compositions containing from 1% to 12%, preferably from 3% to 10%, nonionic surfactant are preferred.

The preferred nonionic surfactant preferably comprises a mixture of alkoxylated alcohols of the formula R (R'O) xOH where R represents a hydrocarbon group (English: hydrocarbyl) containing from 12 to 20 carbon atoms, R'0 represents an alkoxy group, preferably a ethoxy group and x is from 4 to 12. I

7 DK 175476 B1

The invention will now be described in further detail in the form of the following examples.

Example 1 5 3240 g of Gelatin (Bloom Strength 0) and 3240 g of sugar were added with stirring to a solution of 1300 g of zinc phthalocyanine sulphate in 5200 g of water. 650 g of coconut oil was emulsified in the solution thus obtained.

The solids content of the mixture thus prepared was approx. 60%, with approx. 16% was zinc phthalocyanine sulfonate and the viscosity was 0.096 Ns / m 2 (96 cp) at 55 ° C.

The mixture was spray-dried in a spray-drying tower during the simultaneous introduction therein of corn starch as a pulverizing composition.

The mixture was introduced at a rate of 2 Ι / min and the temperature in the spray drying zone was approx. 70 ° C.

20

The final product (about 9200 g) was sieved and the 30 mesh - 120 mesh (ASTM) fraction was collected and analyzed. The collected fraction contained 14.1% zinc phthalocyanine sulfonate, and the average particle diameter was approx. 350 Mm.

25

EXAMPLE 2 2388 g of Gelatin was dissolved in 2135 g of water with stirring and heating to a temperature of ca. 60 ° C. A solution of 126 g of sodium hydroxide in 215 g of water was added to the gelatin solution at a temperature of 60 ° C with stirring. After stirring for 20 minutes at 60 ° C, 135 g of concentrated sulfuric acid (96%) was added and the pH was adjusted to ca. 5.5. 900 g of the solution thus obtained ("hydrolyzed gelatin") was mixed with stirring with a solution of 100 g of zinc phthalocyanine sulfonate in 1150 g of water, 450 g of spray-dried glucose syrup (Mor-sweet® 1924) and 50 g of coconut oil at 55 ° C. When the coconut oil had been emulsified in the aqueous medium, an additional amount of water of 700 g was added. The solids content of the mixture thus obtained was approx. 30%, with approx.

In DK 175476 B1 I 8 In 10% was zinc phthalocyanine sulfonate. The viscosity of the mixture was approx.

m o r \ I

At 0.05 Ns / ra (50 cp) at 60 C. The mixture was spray dried in one

conventional spray drying tower at an inlet temperature of 240 ° C

I and an outlet temperature of 97 ° C.

In the spray-dried product (about 900 g) was sieved and the sieve fraction having a cell size smaller than 100 mesh (ASTM) was sieved.

I collected. IN

This fraction contained 9.7% zinc phthalocyanine sulfonate, and the average particle size was approx. 50 tender.

Example 3 I

In 1060 g of gum arabic and 1010 g of sugar (sucrose) remained below 1

Stirring was added to a solution of 1375 g of zinc phthalocyanine sulfonate in 1

In 1,850 g of water. 138 g of coconut oil was emulsified in the thus I

In obtained solution. IN

The solids content of the mixture thus prepared was approx. 45%, I

In that approx. 11.4% was zinc phthalocyanine sulfonate and viscosity I

At 0.108 Ns / m2 (108 cp) at 57 ° C.

The mixture was spray-dried in a spray-drying tower during mixing.

In the introduction of corn starch therein as a pulverization composition. IN

In Blandignen was introduced at a rate of 1.5 min / min., And tempera- ture

In the trip in the spray drying zone was approx. 65 ° C. IN

In the final product (about 3500 g) was sieved and 30 mesh - 170 mesh (ASTM) in the fraction was collected and analyzed.

In the collected fraction, 8.2% contained zinc phthalocyanine sulfonate, and I

In the average particle diameter, approx. 250 pm.

I 35

In Example 4 I

In 1060 g of Gelatin (Bloom strength 0) and 1010 g of sugar (sucrose) I were added with stirring to a solution of 1250 g of aluminum.

DK 175476 B1 I

phthalocyanine sulfonate in 850 g of water. 138 g of coconut oil was emulsified

in the solution thus obtained. IN

The solids content of the mixture thus prepared was approx. 53%, I

5 as approx. 6.3% was aluminum phthalocyanine sulfonate and viscosity was 1

0.106 Ns / mZ (106 cp) at 58 ° C. IN

The mixture was spray-dried in a spray-drying tower during the same time

you introduce therein corn starch as a pulverization composition. IN

10 I

The mixture was introduced at a rate of 1.5 Ι / min, and the temperature in the spray drying zone was approx. 70 ° C.

In the final product (about 2800 g), the sieve was sieved and 30 mesh - 170 mesh (ASTM) in the 15 fraction was collected and analyzed. The collected fraction I contained 5.2% aluminum phthalocyanine sulfonate.

In Example 5, 2060 g of gum arabic and 1010 g of spray-dried glucose syrup (Mor-Sweet® 1924) were added with stirring to a solution of 1250 g of aluminum phthalocyanine sulfonate in 2350 g of water. 138 g of coconut oil were emulsified in the solution thus obtained.

In the dry matter content of the mixture thus prepared was approx. 40%, with approx. 6.3% was aluminum phthalocyanine sulfonate and the viscosity was I 0.104 Ns / m 2 (104 cp) at 58 ° C.

I. The mixture was spray-dried in a spray-drying tower during simultaneous introduction therein of corn starch as a powdering composition.

The mixture was introduced at a rate of 1.5 Ι / min, and the temperature in the spray drying zone was approx. 70 ° C, I The final product (about 3100 g) was sieved and 30 mesh - 170 mesh (ASTM) in the fraction was collected and analyzed. The collected fraction I contained 4.2% aluminum phthalocyanine sulfonate.

I DK 175476 B1 I

I 10 I

In Example 6 I

In Oer, a granular detergent composition was prepared having the following I

In 5 composition. IN

In Component% I

Talgal cool sul fat 2.4 I

In 10 Linear all cool benzene sulphonate 5.6 I

In Polymer 2.0 I

In Silicate 8.0 I

In sodium tripolyphosphate 21.0 I

In Sodium Perborate 15.0 I

In 15 Nonionic Surfactant ("Dobanol" 45E7) 5.0 I

In Enzyme (protease) 0.8 I

I TAED 2.0 I

I Zinc phthalocyanine sulfonate * 0.03 I

20 Minor Components (Optical White, I

In chelating agents, CMC, perfume, antifoam); IN

In inorganic salts (sodium sulfate, I

In sodium carbonate, magnesium sulfate); IN

In and water The rest I

I 25 I

* Encased in "zero-bloom" gelatin, the capsule's ZPS content 3.4%. IN

Capsule particle size 150-450 µm; 0.88% is added to I

obtaining a ZPS content of 0.03 in the detergent composition. IN

30 * I 1

Claims (17)

A photoactivator dye composition, characterized in that it comprises mi crocapsules, is of a solid dispersion of a water-soluble photoactive ivator dye in an encapsulating material, which is rapidly soluble in water, wherein the microcapsules are weighted on the basis of the capsules comprising: a) % to 60% photoactivator dye, 10 b) from 38% to 97% encapsulating material and c) from 2% to 12% water. Composition according to claim 1, characterized in that the encapsulating material is insoluble in non-ionic surfactants. Composition according to claim 1 or 2, characterized in that it comprises microcapsules having an average particle size of from 50 µm to 450 µπι. Composition according to claim 1 or 2, characterized in that the photoactivator dye is a polyvalent metal ion complex of sulfonated phthalocyanine. 25 Composition according to claim 4, characterized in that the photoactivator dye is zinc phthalocyanine sulfonate, aluminum phthalocyanine sulphonate or a mixture thereof. Composition according to claims 2-5, characterized in that the encapsulating material is selected from hydrolyzed gelatin and hind-forming carbohydrates, including dextrin and gum arabic. Composition according to claims 1-6, characterized in that 35 ml of croc capsules comprise from 1% to 40% by weight of photoactivator dye. Composition according to claims 1-7, characterized in additionally containing sucrose or glucose syrup, wherein the weight to weight ratio of encapsulating material to sucrose or glucose-IB syrup is at least 35:65, preferably 50:50. IN Process for preparing the photoactivator composition In fl 5 according to claim 1 or 2, characterized in, In fl (1) a photoactivator dye is dissolved in an aqueous medium, In fl (2) the photoactivator dye solution is mixed with an aqueous I fl 10 solution of the encapsulating material. In fl (3), the mixture thus obtained is converted into droplets having an average IB particle size not exceeding 500 µm, and in fl 15 (4) the moisture content of the particles is reduced to a value of 1 fl between 2 wt% and 12 wt% to forming a solid II solution of the photoactivator dye in the encapsulating material. I I 20 Process according to claim 9, characterized in that the conversion of the mixture into droplets and the reduction of the droplet moisture content of the droplets is carried out by spray drying. IN Process according to claim 10, characterized in that the spray drying is carried out. at a temperature of less than 100 ° C, during the introduction of a fine powder into the spray drying zone. IN Process according to claim 9, characterized in that the spray spray drying is carried out at a temperature above 100 ° C. I I 30 I fl Process according to claims 9-12, characterized in that I in sucrose or glucose is added to the mixture of the photoactivator-dye and the encapsulating material. I I 35 Process according to claims 9-13, characterized in that I in an oil is emulsified in the mixture of the photoactivator dye and I in the encapsulating material. IN Detergent composition, characterized in that it comprises: a) a surfactant, b) a photoactivator dye composition according to any one of claims 1-6, wherein the pure photoactivator dye is present in an amount of 2 ppm to 1000 ppm of the total composition, and c) the residue made up of traditional detergent ingredients. Detergent composition according to claim 15, characterized in that it comprises from 1% to 12% non-ionic surfactant. Detergent composition according to claim 16, characterized in that the nonionic surfactant comprises a mixture of alkoxylated alcohols of the formula R (R'O) xOH, wherein R represents a hydrocarbon group having from 12 to 20 carbon atoms, R '0 represents an alkoxy group and x is from 4 to 12. 20 25 in 30 1